Simple contagion requires you to only be exposed to it once to be transmitted, whilst complex contagion demands multiple exposures for transmission.
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For simple contagions, it's often ideas that are familiar, products that we already really know, things that make sense to us intuitively. And so when we see a new one, it's not a lot of work emotionally or cognitively or in any other way to just adopt it and pass it on. Examples of this can include seeing memes and videos online and sharing it with others.
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Complex contagion's, by contrast, are the kinds of social change initiatives or the kinds of ideas or the kinds of products that are less familiar, and where it often requires people to change their behaviour in some important way. Examples of this include recycling more or practicing safe sex.
Complex contagions often require reinforcement not just from one, but from multiple people, whilst the quality and strength of the relationship of who you're hearing this from is an important factor too.